CN101733019B - Microporous membrane reinforced fluorine-containing crosslinked and doped ion exchange membrane and preparation method thereof - Google Patents

Microporous membrane reinforced fluorine-containing crosslinked and doped ion exchange membrane and preparation method thereof Download PDF

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CN101733019B
CN101733019B CN2009102311644A CN200910231164A CN101733019B CN 101733019 B CN101733019 B CN 101733019B CN 2009102311644 A CN2009102311644 A CN 2009102311644A CN 200910231164 A CN200910231164 A CN 200910231164A CN 101733019 B CN101733019 B CN 101733019B
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film
ion exchange
membrane
amberplex
microporous barrier
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CN101733019A (en
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张永明
唐军柯
刘萍
张恒
王军
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Shenzhou New Material Co Ltd
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Abstract

The invention relates to a microporous membrane reinforced perfluoro crosslinked and doped ion exchange membrane, belonging to the field of functional polymer composites. The ion exchange membrane takes the microporous membrane as a reinforcer, contains auxiliary proton conducting substances and takes perfluoro ion exchange resins as membrane-forming resins. Triazine ring chemical crosslinking structures are formed among the perfluoro ion exchange resins and the acidic groups on the crosslinking structures are physically bonded and crosslinked with added high-valence metal compounds, thereby forming a dual network structure. The ion exchange membrane prepared by the invention has excellent pyroconductivity and dimensional stability, good mechanical strength and stability and especially excellent gas permeation resistance.

Description

Fluorine-containing cross-linked doped amberplex that a kind of microporous barrier strengthens and preparation method thereof
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of microporous barrier and strengthen fluorine-containing cross-linked doped amberplex and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the TRT of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to PEM.
Now the perfluorinated sulfonic acid PEM that uses have good proton-conducting and chemical stability under (80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives:, poor chemical stability not high as poor dimensional stability, mechanical strength etc.Film water absorption rate and size of causing because of suction under different humidity expand also different, and when film during at different operating mode down conversion, the size of film also will so change.So repeatedly, finally cause PEM generation mechanical damage.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules causes film generation chemical degradation and damaged, foaming.At last, when the operating temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes impatient acute decline of the proton conducting of film.But high operating temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in DMFC, methanol permeability is very big, and this becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. and become the key subjects that fuel cell industries faces.
In the U.S. Pat 5834523 (Ballard company) the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, methyl alcohol/the propanol solution of β-trifluorostyrene copolymer is immersed in the hole of porous PTFE film of swelling, dries under 50 ℃ then, obtains composite membrane.
Adopt mass concentration to be 5% perfluor sulfoacid resin solution and to add the wetability that a certain amount of non-ionic surface active agent strengthens solution among the US5547551, promote the immersion of perfluorinated resin fenestra in the PTFE microporous barrier.With brush mixed solution is brushed on the thick polytetrafluoroethylene (PTFE) varicosity of 20 μ m, after 140 ℃ of processing, composite membrane is immersed in the activating agent that removes in the isopropyl alcohol in the striping.
But the film of filling how empty film system by perfluorinated sulfonic resin often has shortcomings such as filling is incomplete, thereby makes film that very high gas permeability be arranged.
Crosslinking technological can improve the mechanical strength of the heat endurance of polymer, the swelling that reduces solvent, raising polymer, and therefore, crosslinking technological has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing defective of perfluorinated sulfonic acid PEM, explored and studied multiple crosslinking technological.
US20070031715 has described the cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride, formed in the method sulphonyl acid anhydride cross-linked structure can improve the mechanical strength of film effectively, but this cross-linked structure has significant disadvantages: sulphonyl acid anhydride unit is unsettled to alkali.
US20030032739 reaches crosslinked purpose by connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell that can reduce film well, but for obtaining the required a lot of steps of this cross-linked structure, not suitability for industrialized process.
US6733914 discloses the perfluor sulfonyl fluorine type film that will melt extrude and has soaked in ammoniacal liquor, thereby forms the PEM of sulfimide cross-linked structure, and so the perfluoro sulfonic acid membrane of handling has excellent mechanical intensity and dimensional stability.But utilizing the resulting film of this method will be uneven film, because ammonia enters film by the method for infiltration, ammonia meeting and sulfuryl fluoride react in the process of infiltration, the sulfuryl fluoride of reaction will stop the further diffusion of ammonia to film inside, thereby form very high crosslink density on the surface of film, and that the inside of film does not take place almost is crosslinked.The big crosslinked electrical conductivity of film that makes in surface sharply descends.
CN200710013624.7 and US7259208 disclose and have contained triazine ring cross-linked structure perfluoro sulfonic acid membrane, have excellent mechanical intensity and dimensional stability equally.
For solving the high temperature proton conduction behavior of sulfonic fluoropolymer film, the inorganic additive that much has the high-temp water-preserving ability is joined in the sulfonic fluoropolymer exchange membrane.The inorganic water conservation particle of choosing need satisfy following performance: (1) particle has water holding capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conductivity; (4) be easy to obtain littler nanometer particle; (5) structural stability of particle is good, does not follow tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of PEM.The inorganic water conservation particle that adopts is SiO normally 2, TiO 2, Zr (HPO 4) 2Or ZrO 2Particle, heteropoly acid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
For example, Chinese patent CN1862857 discloses in the sulfonic fluoropolymer resin and has added SiO 2Etc. inorganic water-loss reducer, can improve the high-temperature electric conduction performance of PEM.
J.Electrochem.Soc. (V154,2007, described Nafion resin and basic zirconium phosphate composite membrane-forming in p.B288-B295).This film still has very high electrical conductance in relative humidity less than 13%.
But adding inorganic water-loss reducer tends to make film strength to reduce.And chemical crosslinking often can not obtain the higher degree of cross linking, thereby these measures can not fundamentally solve the use problem of film.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer descends, and (equivalent value EW value reduced, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, and this will produce very fuel cell and seriously influence.Therefore, the film that preparation has the macroion exchange capacity, have good Mechanics of Machinery intensity and air-tightness, have good stability is a fuel cell, is to make the battery that uses on the delivery vehicle such as automobile be able to practical key.
Summary of the invention
At the deficiencies in the prior art, the inventor after having paid creative work, has finished the present invention through further investigation.The invention provides a kind of microporous barrier and strengthen the cross-linked doped perfluorinated ion-exchange membrane of triazine ring.This amberplex is characterised in that: the perfluorinated ion exchange resin that will be added with auxiliary proton conductive substance is filled in the microporous barrier, the intermolecular of perfluorinated ion exchange resin is cross-linked with each other simultaneously, form triazine ring chemical crosslinking structure, and it is crosslinked that acidic-group on this cross-linked structure and high-valency metal compound form physical bond, thereby form dual network structure, described triazine ring chemical crosslinking structure is suc as formula (I):
Figure G2009102311644D00031
The structure of high-valency metal compound [is example with the Ce ion] and acidic exchange group physical bond is shown in (II)
Figure G2009102311644D00032
Described perfluorinated ion exchange resin be by tetrafluoroethene, one or more contain the perfluor alkene monomer of acidic exchange group and perfluor alkene monomer copolymerization that one or more contain crosslink sites forms, or the mixture of one or more above-mentioned copolymers; The EW value of described ion exchange resin is not special to be limited, and for example can be 600～1300, is preferably 700～1200.
This copolyreaction is the common practise in the organic chemistry field of polymer technology, as long as clear and definite comonomer specifically, then to those skilled in the art, select suitable copolyreaction condition according to prior art with may be obvious that, as temperature, time, solvent, initator etc., thereby obtain perfluorinated ion exchange resin of the present invention.
The described perfluor alkene monomer that contains the acidic exchange group is selected from following formula (A) or (B):
CF 2＝CFO[CF 2CF(CF 3)] fO(CF 2) gSO 3H
F=0 or 1; The integer of g=2～4 (A)
CF 2＝CFO(CF 2) 3PO 3H 2 (B)
The described fluorine-containing alkene monomer that contains crosslink sites is selected from following formula (IX) or (X):
F 2C＝CFR f4Y 4
(IX)
Figure G2009102311644D00033
Wherein, Y 4, Y 5Be selected from CN;
A ', b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X 1Be selected from F or CN;
N ' is 0 or 1;
R F4, R F5, R F6Be perfluoroalkyl independently, preferred C 1-C 5Perfluoroalkyl.
Preferably, described ion exchange fluoro resin is surface-crosslinked microporous barrier, or crosslinked in the space of microporous barrier.
Described microporous barrier is organic micro film or inorganic microporous barrier, and the aperture is 0.1～5 μ m, is preferably 0.5～4 μ m, most preferably is 1～3 μ m; Thickness is 5～100 μ m, is preferably 10～80 μ m, most preferably is 20～60 μ m; Porosity is 30～99%, is preferably 40～80%, most preferably is 50～70%.
Organic micro film preferred polymers microporous barrier wherein is as the fluorocarbon polymer film; Inorganic microporous barrier is preferably ultra-thin Si O especially 2Film, TiO 2Film, ZrO 2Film or cellular glass film etc.More preferably, organic micro film is selected from eptfe film, expanded microporous polytetra fluoroethylene-EPTEE-hexafluoropropene film, porous tetrafluoroethene-perfluoroalkyl ethylene oxy copolymer or porous polyimide film; Inorganic microporous barrier is selected from porous Al 2O 3The ZrO2 microporous barrier of film, phosphoric acid modification, the sulfuric acid modified ZrO that gets 2Microporous barrier, improved silica microporous barrier, micropore glass film film or molecular sieve film.
Described microporous barrier preferably carries out hydrophilic modifications such as surface silicon acidifying, sulfonation, sulphation, phosphorylation.
For example concerning the fluorocarbon polymer film, can silicify to the surface, modification such as sulfonation, sulphation, phosphorylation.Existing surface modifying method for polytetrafluoroethylene (PTFE) all is suitable for the modification to the fluorocarbon polymer film, comprises reduction modification method, laser emission modification method, plasma modification method and the silicic acid activation method of sodium naphthalene solution.Wherein preferred silicic acid activation method is because it can be at the silica that directly deposits water conservation on the fluorocarbon polymer film surface.By fluorocarbon polymer film surface after the modification hydrophilic group has been arranged, but has preferably further carried out modification on this basis again, as with the fiber of modification at ethyl orthosilicate, ZrOCl 2-H 3PO 4Or carry out further modification in the titanate esters etc.
And, then these inorganic microporous barriers directly can be positioned over ethyl orthosilicate, ZrOCl for the surface modification of inorganic microporous barrier 2-H 3PO 4, titanate esters, H 3PO 4, H 2SO 4Deng in carry out modification, also can when the synthesizing inorganic microporous barrier, add modifier directly to generate the modified inorganic microporous barrier, for example phosphate and ethyl orthosilicate are mixed, become Modified Membrane with the alkali gel.For example, prepare the concrete grammar of silica modified voided polytetrafluoroethylene film, exactly voided polytetrafluoroethylene film is placed on SiCl 4Be warmed up to 110 ℃ and kept 1 hour in the atmosphere after 1 hour, be cooled to 60 ℃ again after, water spray is handled and is obtained silica modified voided polytetrafluoroethylene film.
Silica modified cellular glass film method is for to place Ti (OEt) with the cellular glass film 4In/the water mixed system, add concentrated ammonia liquor down in stirring, hydrolysis is left standstill and is obtained the cellular glass film that titanium dioxide is modified.Also can be with inorganic ultrathin membrane such as TiO 2Film, ZrO 2Film is directly at H 3PO 4Or H 2SO 4Soak Deng in the inorganic acid, thereby carry out surface modification.
The preparation method who also has a kind of modified inorganic ultrathin membrane of separating out jointly, as triethyl phosphate is mixed with ethyl orthosilicate (1: 100 mass ratio), add entry and concentrated ammonia liquor then and left standstill gel 12 hours, utilize surfactant such as hexadecyltrimethylammonium chloride to make the lamina membranacea gel then, obtain the ultra-thin silicon dioxide film of phosphoric acid modification.
Because perforated membrane carried out the surface active modification, have acidity or functional group and make and to form strong crosslinked action by the physical bond of high-valency metal compound between perforated membrane and the film-forming resin.
Described auxiliary proton conductive substance specifically is selected from one of following or combination:
(1) oxide is shown in general formula: QO E/2E=1～8; Wherein Q be second and third, four, five major element or transition elements, concrete as: SiO 2, Al 2O 3, Sb 2O 5, SnO 2, ZrO 2, TiO 2, MoO 3Or OsO 4
(2) phosphate, comprise first, second, third and fourth, the various forms of orthophosphates and the condensed phosphate of five major elements, transition elements; Concrete as: BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, HZr 2(PO 4) 3, Ce (HPO 4) 2, Ti (HPO 4) 2, KH 2PO 4, NaH 2PO 4, LiH 2PO 4, NH 4H 2PO 4, CsH 2PO 4, CaHPO 4, MgHPO 4, HSbP 2O 8, HSb 3P 2O 14, H 5Sb 5P 2O 20, Zr 5(P 3O 10) 4Or Zr 2H (P 3O 10) 2
(3) polyacid, multi-acid salt and hydrate thereof are shown in general formula: A iB jC kO lMH 2O; Wherein A be one, two, three, four, the pentavalent group first, second, third and fourth, five major elements or transition elements; B, C can be second and third, four, five, six, seven major element or transition elements; I=1～10, j=0～50, k=0～50, l=2～100, m=0～50.As: H 3PW 12O 40α H 2O (α=21-29), H 3SiW 12O 40β H 2O (β=21-29), H xWO 3, HSbWO 6, H 3PMo 12O 40, H 2Sb 4O 11, HTaWO 6, HNbO 3, HTiNbO 5, HTiTaO 5, HSbTeO 6, H 5Ti 4O 9, HSbO 3Or H 2MoO 4
(4) silicate comprises zeolite, NH 4 +The zeolite, phyllosilicate, web-like silicon hydrochlorate, H-sodalite, H-modenite, the NH that handle 4-analcime, NH 4-sodalite, NH 4-gallate or H-montmorillonite;
(5) sulfate is shown in general formula: D oH pS qO rWherein D can be one, two, three, four, the pentavalent group first, second, third and fourth, five major elements or transition elements; O=1～10, p=0～10, q=1～5, r=2～50; As: CsHSO 4, Fe (SO 4) 2, (NH 4) 3H (SO 4) 2, LiHSO 4, NaHSO 4, KHSO 4, RbSO 4, LiN 2H 5SO 4Or NH 4HSO 4
(6) selenite and arsenide are shown in general formula: E sH tF uO vWherein A can be one, two, three, four, the pentavalent group first, second, third and fourth, five major elements or transition elements; F can be As or Se; S=1～10, t=0～10, u=1～5, v=2～50; As: (NH 4) 3H (SeO 4) 2, (NH 4) 3H (SeO 4) 2, KH 2AsO 4, Cs 3H (SeO 4) 2Or Rb 3H (SeO 4) 2
Most preferably, described auxiliary proton conductive substance is selected from: SiO 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, CsHSO 4, H-montmorillonite, CsH 2PO 4, HZr 2(PO 4) 3, Ti (HPO 4) 2, H 3PW 12O 40, or Zr 2H (P 3O 10) 2In one or more.
The mass ratio of described auxiliary proton conductive substance and perfluorinated ion exchange resin is 0.5～50: 100, is preferably 1～40: 100, more preferably 5～30: 100; Its particle diameter is 0.001～5 μ m, is preferably 0.01～4 μ m, and more preferably 0.1～3 μ m most preferably is 0.5～2 μ m.
The metallic element of described high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element, these element compounds account for perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.01～4%, more preferably 0.1～3%.。
Described high-valency metal compound can load on the auxiliary proton conductive substance.
Described high-valency metal compound can be selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate or the acetate of the highest price attitude of these metallic elements and middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or DMSO (dimethyl sulfoxide (DMSO)) complex compound of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state, comprises but is not only following Compound C e xTi (1-x)O 2(x=0.25～0.4), Ca0.6La 0.27TiO 3, La (1-y)Ce yMnO 3(y=0.1～0.4) or La 0.7Ce 0.15Ca 0.15MnO 3
The present invention also provides the preparation method of described ionic membrane, comprises the steps:
1) will contain the perfluorinated ion exchange resin, crosslinking catalyst of crosslink sites, auxiliary proton conductive substance and high-valency metal compound, make suspension liquid, then by solution-cast, curtain coating, silk-screen printing technique, spraying or impregnation technology and enhancing porosity composite membrane-forming;
(2) between film forming stage or carry out crosslinkedly after the film forming, form the cross-linked structure shown in the formula (I);
The method that forms (I) cross-linked structure is that the sulfonic fluoropolymer resin in cyano-containing site forms under hot or sour effect.Described acid is strong protonic acid or lewis acid; Wherein said Bronsted acid is selected from H 2SO 4, CF 3SO 3H or H 3PO 4Described lewis acid is selected from ZnCl 2, FeCl 3, AlCl 3, organo-tin compound, organo-antimony compound or organic tellurium compound.
Strengthen in the cross-linked doped perfluorinated ion-exchange membrane of triazine ring structure at microporous barrier of the present invention, the multiple means such as physical cross-linked network of using microporous barrier, triazine ring structure cross-linked network and high-valency metal compound and acidic exchange group to form, act synergistically simultaneously, improved the mechanical strength of ionic membrane.The present invention has overcome shortcomings such as caused film leakiness, air penetrability height when only using microporous barrier to strengthen, and has also overcome the not high shortcoming of the crosslinked degree of cross linking when only using chemical bonding.On the basis of microporous barrier enhancing and the modification of triazine ring cross-linked network, by the physical cross-linked network of using high-valency metal compound and acidic exchange group to form, (its improvement degree strengthens far above microporous barrier and the film of triazine ring cross-linked network modification in the stability of thickness direction at the dimensional stability of length and width direction and film not only to have increased film greatly, Chinese patent 200810138427.2), a bit be that what not expected is that the chemical stability of film also improves greatly in addition, trace it to its cause, the abnormal compact because film becomes under the effect of multiple crosslinking method, fuel gas not only, oxidizing gas can not penetrate into film, and those have the material such as the H of high oxidation 2O 2With free radical also can't be by diffusing in the film, thereby guarantee film chemical stability.
The specific embodiment
By the following examples the present invention is further specified, but those skilled in the art as can be known, the following examples only are used to explain, and are not that the spirit and scope of the present invention are limited.
Embodiment 1:
With repetitive be
Figure G2009102311644D00061
, EW=800 fluoropolymer resin and repetitive be
Figure G2009102311644D00062
, EW=1200 fluoropolymer resin press mass ratio 2: 3 and mix, be the SiO of 0.03 μ m again with granularity 2(SiO 2With the mass ratio of two kinds of perfluorinated sulfonic resins be 5: 100), tetraphenyltin, granularity be the Zr (HPO of 0.005 μ m 4) 2(Zr (HPO 4) 2With the mass ratio of two kinds of resins be 3: 100) and carbonic acid vanadium (account for total resin quality 0.01%) be dispersed in propyl alcohol-water, make total mass concentration and be propyl alcohol-aqueous solution of 5%, the thickness that immerses the silicic acid modification is the porous hexafluoropropene film (porosity is 94%) of 30 μ m, obtains cross-linking ion membrane.
Embodiment 2:
With repetitive be
Figure G2009102311644D00071
, EW=700 fluoropolymer resin, repetitive is
, EW=1300 fluoropolymer resin (two kinds of resin quality ratios are 1: 0.2), phenyl stannic hydroxide, 8-hat-6-Y complex compound (account for resin quality 0.3%) and granularity be the ZrO of 10nm 2(is 2: 100 with the mass ratio of two kinds of fluoropolymer resins) mixes, being dissolved into then and making total mass concentration among the DMF is 20% solution, be that 50 μ m and porosity are that 75% micropore glass film film places above-mentioned solution to soak about 3 hours then with thickness, heat to such an extent that thickness is the individual layer perfluorinated sulfonic acid cross-linking ion membrane of 50 μ m.
Embodiment 3:
With repetitive be
Figure G2009102311644D00073
, EW=1200 fluoropolymer resin, triphenyl tin hydroxide and the surface by perovskite structure La 0.7Ce 0.15Ca 0.15MnO 3The granularity of modifying is the ZrO of 8 μ m 2(with the mass ratio of resin be 2: 100) be scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, handled 60 minutes down at 170 ℃, make the cross-linking ion membrane that thickness is 20 μ m.
Embodiment 4:
With repetitive be
Fluoropolymer resin and repetitive be
Figure G2009102311644D00081
Fluoropolymer resin be that 1: 5 ratio is mixed in mass ratio, zinc hydroxide (account for resin quality 2%) and ZrO 2(particle diameter 0.01 μ m) is to mix at 100: 9 by mass ratio, then these two kinds of mixtures are scattered in the N-methyl pyrrolidone that to form solid masses content be 30% dispersion liquid, in solution, add a spot of antimony organic catalyst again, with the thick and porosity of 80 μ m is that 65% expanded ptfe film places above-mentioned solution to soak half an hour approximately, 230 ℃ of following film forming.
Embodiment 5:
With repetitive be
, the fluoropolymer resin of EW=700 and the fluoropolymer resin (two kinds of resin quality ratios are 1: 4) of embodiment 3, tetraphenyltin, yttrium nitrate (account for total resin quality 0.2%), granularity are the ZrO of 5 μ m 2(with the mass ratio of total resin be 2: 100) be scattered in the dimethyl sulfoxide (DMSO), (diameter is 0.5 μ m to polytetrafluoroethylporous porous membrane by silk-screen printing technique method and phosphoric acid modification, thickness is 20 μ m, voidage 85%) carry out compoundly, obtain the film that thickness is 25 μ m.
Embodiment 6:
With repetitive be
Figure G2009102311644D00083
, EW=1200 fluoropolymer resin, the phenyl stannic hydroxide, cyclodextrin-Ru (for resin quality 1%) and granularity be the Ce (HPO of 8 μ m 4) 2(with the mass ratio of resin be 2: 100) be scattered among the DMF, place above-mentioned solution to soak half an hour approximately the thick porous polyimide film of 20 μ m, handled 60 minutes down at 170 ℃, make the cross-linking ion membrane that thickness is 20 μ m.
Comparative example 7
Utilizing mass concentration is 10% nafion
Figure G2009102311644D00084
Solution, the eptfe film that 30 μ m are thick (porosity is 70%) place above-mentioned solution to soak about 1 hour, and the film that will soak carries out the drying processing on 170 ℃ of heating plates then, obtain the thick microporous barrier of 30 μ m and strengthen amberplex.
Experimental example 8
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, be added with 95 ℃ of electrical conductivity, hot strength, the hydrogen permeate electric current of the triazine ring cross-linked doped ion-exchange membrane that the microporous barrier of high-valency metal compound strengthens, performances such as size changing rate all are better than the film that common microporous barrier strengthens amberplex and do not increase divalent metal compound, and the raising and the improvement of highly significant have especially been arranged aspect gas permeation resistance.
The various films of table 1 characterize
Figure G2009102311644D00091

Claims (6)

1. a microporous barrier strengthens the cross-linked doped perfluorinated ion-exchange membrane of triazine ring, it is characterized in that: the perfluorinated ion exchange resin that will be added with auxiliary proton conductive substance is filled in the microporous barrier, the intermolecular of perfluorinated ion exchange resin is cross-linked with each other simultaneously, form triazine ring chemical crosslinking structure, and it is crosslinked that acidic-group on this cross-linked structure and high-valency metal compound form physical bond, thereby form dual network structure, described triazine ring chemical crosslinking structure is suc as formula (I):
Figure FSB00000405180200011
The metallic element of wherein said high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element; And
Described high-valency metal compound is selected from a kind of in nitrate, sulfate, carbonate, phosphate or the acetate of the highest price attitude of these metallic elements and middle valence state;
Or be selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, EDTA, DMF or the DMSO complex compound of middle valence state;
Or be selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state;
Or be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state; Described oxide with perovskite structure is Ca 0.6La 0.27TiO 3, La (1-y)Ce yMnO 3Or La 0.7Ce 0.15Ca 0.15MnO 3, y=0.1～0.4 wherein;
Described perfluorinated ion exchange resin is to be formed by tetrafluoroethene, one or more perfluor alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain the acidic exchange group;
The described perfluor alkene monomer that contains the acidic exchange group is selected from formula (A) or (B):
CF 2＝CFO[CF 2CF(CF 3)] fO(CF 2) gSO 3H
F=0 or 1; The integer of g=2～4 (A)
CF 2＝CFO(CF 2) 3PO 3H 2 (B)
The described perfluor alkene monomer that contains crosslink sites is the structure of formula (X):
Figure FSB00000405180200012
Wherein, Y 5Be selected from CN;
A ', b ', c ' they are 0 or 1 independently, but a '+b '+c ' ≠ 0;
X 1Be selected from F or CN;
N ' is 0 or 1;
R F5, R F6Be perfluoroalkyl independently.
2. amberplex as claimed in claim 1 is characterized in that: described R F5, R F6Be C independently 1-C 5Perfluoroalkyl.
3. amberplex as claimed in claim 1 or 2 is characterized in that: described microporous barrier is selected from eptfe film, expanded microporous polytetra fluoroethylene-EPTEE-hexafluoropropene film, porous polyimide film, SiO 2Film, TiO 2Film, ZrO 2Film, Al 2O 3Film or cellular glass film.
4. amberplex as claimed in claim 1 or 2 is characterized in that: described auxiliary proton conductive substance is selected from: SiO 2, ZrO 2, TiO 2, BPO 4, Zr 3(PO 4) 4, Zr (HPO 4) 2, H 3PW 12O 40, CsHSO 4, CsH 2PO 4, H-modenite, H-montmorillonite, HZr 2(PO 4) 3, Ce (HPO 4) 2, Ti (HPO 4) 2Or Zr 2H (P 3O 10) 2In one or more.
5. amberplex as claimed in claim 1 or 2 is characterized in that: described high-valency metal is compound loaded on auxiliary proton conductive substance.
6. amberplex as claimed in claim 1 is characterized in that: described crown ether is a nitogen-contained crown ether.
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